Thioester polymerization modifiers
First Claim
1. A polymerizable resin composition comprising:
- at least one polymerizable resin which undergoes exothermic polymerization and which is selected from the group consisting essentially of at least one unsaturated monomer and unsaturated polyester resins, vinyl ester resins and mixtures thereof; and
a substantially non-polymeric ester of a thiocarboxylic acid mixed with said resin in an effective amount to substantially reduce the exothermic heat generated during free radical polymerization of said resin, but insufficient to substantially reduce the exothermic heat generated during free radical polymerization of said resin, but insufficient to substantially affect the degree or rate of free radical polymerization of said resin, said ester of a thiocarboxylic acid having the formula ##STR14## in which Z is an alkyl having 1-18 carbon atoms or Z is ##STR15## and where a is 1, b is a whole number from 1 to about 5, n is a whole number from zero to b, and R is an alkyl or hydroxyalkyl having 1-18 carbon atoms and zero to 2 hydroxyl groups, alkyloxyethyl, alkyloxyethoxyethyl, and alkyloxypolyethoxyethyl having 1 to about 30 carbon atoms in the alkyl group;
or when n is zero and Z is alkyl, R is ##STR16## in which Y is an alkylene group having 2 to about 20 carbon atoms or an alkylene group interrupted at intervals or 2 or more carbon atoms by oxygen atoms and having 4 to about 40 carbon atoms and one to 19 oxygen atoms.
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Accused Products
Abstract
A composition and method for the polymerization of polymerizable resins which undergo exothermic polymerization, including unsaturated polyester resins, vinyl ester resins and mixtures thereof, and the polymerized product thereof, wherein an ester of a thiocarboxylic acid is present in a effective amount to substantially reduce the exothermic heat generated during polymerization of the resin, but insufficient to substantially affect the degree or rate of polymerization of the resin. The preferred thioester has the formula ##STR1## in which Z is an alkyl having 1-18 carbon atoms or ##STR2## a is 1 or 2, b is a whole number from 1 to about 5, n is a whole number from zero to b, and R is an alkyl or hydroxyalkyl having 1-18 carbon atoms and zero to 2 hydroxyl groups, alkyloxyethyl, alkyloxyethoxyethyl, and alkyloxypolyethoxyethyl having 1 to about 30 carbon atoms in the alkyl group; or when n is zero and z is alkyl, R is ##STR3## in which Y is an alkylene group having 2 to about 20 carbon atoms or an alkylene group interrupted at intervals of 2 or more carbon atoms by oxygen atoms and having 4 to about 40 carbon atoms and one to 19 oxygen atoms. Preferred specific thioesters include ditridecyl thiodipropionate, dimethyl thiodipropionate, and dimethyl dithiodipropionate.
6 Citations
33 Claims
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1. A polymerizable resin composition comprising:
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at least one polymerizable resin which undergoes exothermic polymerization and which is selected from the group consisting essentially of at least one unsaturated monomer and unsaturated polyester resins, vinyl ester resins and mixtures thereof; and a substantially non-polymeric ester of a thiocarboxylic acid mixed with said resin in an effective amount to substantially reduce the exothermic heat generated during free radical polymerization of said resin, but insufficient to substantially reduce the exothermic heat generated during free radical polymerization of said resin, but insufficient to substantially affect the degree or rate of free radical polymerization of said resin, said ester of a thiocarboxylic acid having the formula ##STR14## in which Z is an alkyl having 1-18 carbon atoms or Z is ##STR15## and where a is 1, b is a whole number from 1 to about 5, n is a whole number from zero to b, and R is an alkyl or hydroxyalkyl having 1-18 carbon atoms and zero to 2 hydroxyl groups, alkyloxyethyl, alkyloxyethoxyethyl, and alkyloxypolyethoxyethyl having 1 to about 30 carbon atoms in the alkyl group;
or when n is zero and Z is alkyl, R is ##STR16## in which Y is an alkylene group having 2 to about 20 carbon atoms or an alkylene group interrupted at intervals or 2 or more carbon atoms by oxygen atoms and having 4 to about 40 carbon atoms and one to 19 oxygen atoms. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 11, 12, 13, 14)
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10. The composition of claim wherein said ester of a thiocarboxylic acid is present in an amount of about 0.5-1.0% by weight of the resin.
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15. A method of reducing the exothermic heat generated during the free radical polymerization of a polymerizable resin which undergoes exothermic polymerization and which is selected from the group consisting essentially of at least one unsaturated monomer and an unsaturated polyester resin, a vinyl ester resin and mixtures thereof, said method comprising:
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mixing a substantially non-polymeric ester of a thiocarboxylic acid with the resin in an effective amount to substantially reduce the exothermic heat generated during polymerization of said resin, but insufficient to substantially affect the degree or rate of polymerization of the resin, said ester of a thiocarboxylic acid having the formula ##STR18## in which Z is an alkyl having 1-18 carbon atoms or Z is ##STR19## and where a is 1, b is a whole number from 1 to about 5, n is a whole number from zero to b, and R is an alkyl or hydroxyalkyl having 1-18 carbon atoms and zero to 2 hydroxyl groups, alkyloxyethyl, alkyloxyethoxyethyl, and alkyloxypolyethoxyethyl having 1 to about 30 carbon atoms in the alkyl group;
or when n is zero and Z is alkyl, R is ##STR20## in which Y is an alkylene group having 2 to about 20 carbon atoms or an alkylene group interrupted at intervals of 2 or more carbon atoms by oxygen atoms and having a 4 to about 40 carbon atoms and one to 19 oxygen atoms;generating free radicals in the mixture to initiate the polymerization of the resin; and polymerizing the resin in the presence of said ester. - View Dependent Claims (16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33)
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Specification